Environmental Research 186 (2020) 109616

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Environmental Research
journal homepage: www.elsevier.com/locate/envres

Biogasoline production from linoleic acid via catalytic cracking over nickel T
and copper-doped ZSM-5 catalysts
Haswin Kaur Gurdeep Singha, Suzana Yusupa,∗, Armando T. Quitainb,c,∗∗, Bawadi Abdullaha,
Mariam Ameena, Mitsuru Sasakib, Tetsuya Kidab, Kin Wai Cheaha
a
Biomass Processing Lab, Center of Biofuel and Biochemical Research, Institute of Self-Sustainable Building, Universiti Teknologi PETRONAS, 32610, Bandar Seri
Iskandar, Perak, Malaysia
b
Faculty of Advanced Science and Technology, Kumamoto University, 2-39-1 Kurokami, Chuo-ku, Kumamoto, 860-8555, Japan
c
International Research Organization for Advanced Science and Technology, Kumamoto University, 2-39-1 Kurokami, Chuo-ku, Kumamoto, 860-8555, Japan

ARTICLE INFO ABSTRACT

Keywords: Catalytic cracking of vegetable oil mainly processed over zeolites, and among all the zeolites particularly HZMS-
Biogasoline 5 has been investigated on wide range for renewable and clean gasoline production from various plant oils.
Catalytic cracking Despite the fact that HZSM-5 offers a higher conversion degree and boost aromatics yield, the isomerate yield
Linoleic acid reduces due to high cracking activity and shape selectivity of HZSM-5. Hence, to overcome these problems, in
Isoparaffin
this study the transition metals, such as nickel and copper doped over HZSM-5 were tested for its efficiencies to
Aromatics
improve the isoparaffin compounds. The catalysts were screened with linoleic acid in a catalytic cracking re-
action conducted at 450 ᵒC for 90 min in an atmospheric condition in batch reactor. Then, the gasoline com-
position of the organic liquid product (OLP) was analysed in terms of paraffin, isoparaffin, olefin, naphthenes
and aromatics (PIONA). The results showed that Cu/ZSM-5 produced the highest liquid yield of 79.1%, at the
same time reduced the production of gas and coke to 18.8% and 0.7%. Furthermore, the desired isoparaffin
composition in biogasoline increased from 1.6% to 6.8% and at the same time reduced the oxygenated and
aromatic compounds to 15.4% and 59.7%, respectively. The linoleic acid as model compound of rubber seed oil,
in the catalytic cracking reaction provides a clearer understanding of the process. Besides, the water gas shift
(WGS) reaction in catalytic cracking reaction provides insitu hydrogen production to saturate the branched
olefin into the desired isoparaffin and the aromatics into naphthenes.

1. Introduction
Recently, The World Energy Outlook Report 2019 (BP, 2019) stated
that the global energy consumption increased rapidly by 2.9% in year
2018. As a result, the carbon emissions also increased at the highest rate
by 2% in seven years. This was primarily attributed by the increase in
the number of passenger cars reflecting the transportation sector. The
rising population and social development are expected to significantly
boost the energy consumption in future. Additionally, the diminishing
petroleum reserves will be insufficient to meet the increasing energy
demand of the coming generation, if alternative solutions are not
considered today.
Renewable energy from biomass is the most promising alternative
solution because biomass derived fuels are categorised as clean and eco-
friendly fuels (Sher et al., 2020). The first generation biofuel such as
bioethanol has been widely used in Brazil replacing the conventional
gasoline to fuel vehicles. Though bioethanol has higher octane number,
evaporation temperature, burning limit and speed, the main limitations
are low energy density, high chances of corrosion, low combustion
luminescence and greater tendency to form azeotropic mixture with
water. Furthermore, a different combustion engine is required for cars
running on bioethanol because the fuel is made of bioalcohols not hy-
drocarbons, resulting in lack of confidence in bioethanol as the new
emerging fuel to substitute the conventional gasoline. Therefore, the
better alternative would be biogasoline due to its similar hydrocarbon
properties to the conventional gasoline and thus can be used directly in
internal combustion engine without engine modification. Furthermore,
it is proven to have a higher combustion energy and is more fuel effi-
cient compared to ethanol.
The selection of technological pathway to produce biogasoline is

∗
Corresponding author.
∗∗
Corresponding author. Faculty of Advanced Science and Technology, Kumamoto University, 2-39-1 Kurokami, Chuo-ku, Kumamoto, 860-8555, Japan.
E-mail addresses: drsuzana_yusuf@utp.edu.my (S. Yusup), quitain@kumamoto-u.ac.jp (A.T. Quitain).

https://doi.org/10.1016/j.envres.2020.109616
Received 31 January 2020; Received in revised form 19 April 2020; Accepted 27 April 2020
Available online 30 April 2020
0013-9351/ © 2020 Elsevier Inc. All rights reserved.
H.K. Gurdeep Singh, et al. Environmental Research 186 (2020) 109616

dependent on the physical state of the feedstock employed. Liquid
feedstock is the most favourable because it produces biogasoline di-
rectly either by catalytic cracking, hydrocracking or thermal cracking
(Ameen et al., 2017). While, the solid feedstock has to be first converted
to syngas via gasification process, bio oil via pyrolysis or liquefaction
process and ethanol via enzyme or acid hydrolysis process prior to
gasoline production by Fischer Tropsch and catalytic upgrading pro-
cess. Nevertheless, catalytic cracking is the most preferred route be-
cause the reactions proceed at a much lower temperature to produce a
higher octane gasoline (Ong and Bhatia, 2010), no hydrogen supply is
required, and the reaction can take place at atmospheric condition.
Hence, this method is considered economical with respect to energy
consumption (Taufiqurrahmi and Bhatia, 2011). Several experimental
setups using fixed bed, fluidized bed and entrained flow reactor have
been used for heterogeneous catalytic cracking reaction. The fluidised
bed reactor is mostly used in petroleum refineries due to short contact
time with catalyst and thus reduces the coke deposition and enhances
the gasoline production. The catalytic reaction using this reactor is
known as fluid catalytic cracking (FCC) reaction (Chew and Bhatia,
2008; Ong and Bhatia, 2010).
The vegetable oils are commonly used for catalytic cracking to
produce biogasoline. Both edible oils for example sunflower, rapeseed,
and palm oil as well as non-edible oils such as jatropha and rubber seed
oil (RSO) have been investigated. However, non-edible oils have shown
high potential based on researchers’ investigation due to food versus
fuel conflicts (Hilten et al., 2011). The rubber seed oil extracted from
the seeds of the rubber tree is a potential non-edible oil source for
biogasoline production. It contains a higher degree of polyunsaturated
fatty acids, particularly linoleic acid which is very suitable for gasoline
production. The reason is because the unsaturated fatty acid decom-
poses and deoxygenates more rapidly than saturated fatty acids. Lino-
leic acid is a polyunsaturated fatty acid with two carbon-carbon double
bonds with a chemical formula of C18H32O2. As a result, RSO is more
suitable for gasoline production than palm oil because the linoleic
composition of RSO (39%) is significantly higher than palm oil (9%)
(Taufiqurrahmi and Bhatia, 2011). Likewise, previous work reported by
Bielansky et al. (2012) concluded that oleic acid (unsaturated fatty
acid) gave a higher gasoline yield compared to palmitic acid (saturated
fatty acid) in the presence of commercial FCC equilibrium catalyst.
Catalyst affects the gasoline yield and composition in the catalytic
cracking reaction. Several researchers have studied various types of
catalyst in the catalytic cracking reaction to produce biogasoline as
shown in Table 1. Among them, zeolite HZSM-5 showed higher gasoline
selectivity as it increased the aromatic content in the organic liquid
product (Taufiqurrahmi and Bhatia, 2011). This was due to its excellent
deoxygenation tendency and shape selectivity. The HZSM-5 catalyst
constitutes of a 3-dimensional intersecting structure with pore size si-
milar to aromatic compounds like toluene, xylene and benzene (Hu
et al., 2017). For that reason, it promotes the formation of aromatics
compounds in gasoline fraction.
Although aromatics boost the fuel's octane number, stringent caps
are imposed by the legislative body on aromatics in a fuel. This is be-
cause fuel rich in aromatics escalates the released of unburnt hydro-
carbons (carbon monoxide) and aromatics (benzene) to the environ-
ment. The carbon monoxide gas causes global warming while benzene
is a proven toxic substance. The carcinogenic property of aromatics
could impair human's health and lead to fatality. Therefore, to over-
come this, the benign isoparaffins compounds are augmented to com-
pensate for the drop in octane quality due to the reduction of the aro-
matics content in fuel (Boot et al., 2017). Besides, further
polymerization of the aromatic compounds causes coke formation re-
sulting in catalyst deactivation during the cracking reaction.
Therefore, several published papers stress the use of metal loading
especially transition metals on ZSM-5 to enhance the active acid sites of
the catalyst owing to their beneficial bifunctional characteristics (acid
and metal function). A study by Vichapund et al. (Vichaphund et al.,
2015) presents the effect of various metals in HZSM-5 such as Ni, Mo,
Ga, Co and Pd on the deoxygenation and hydrogen transfer activity of
the catalyst. Ni and Co favour olefin formation while Mo, Ga and Pd
promote the undesired aromatics formation via dehydrogenation. The
deoxygenating trend reported was Ni > Pd > Co > Mo > Ga.
Hence, nickel enhances deoxygenation reaction and reduces aromatics.
Besides, Zhao et al. (2015a), reported that using Zn/ZSM-5 enhanced
the decarboxylation reaction by producing the highest CO2 yield that
favoured the removal of oxygen. Recently, Ahmad et al. (2016),
claimed that heterometallic nano oxides integrated with ZSM-5
(Fe–Zn–Cu-ZSM-5 (31) gave highest gasoline yield by catalytic cracking
of palm oil.
Though several studies have discussed on various metal modified
ZSM-5 in response to biogasoline, aromatics, coke and oxygenates yield,
the study still lacks in experimenting modified ZSM-5 to increase the
isoparaffin yield in the catalytic cracking reaction. The isomerization
and hydrogenation reaction promote isoparaffin formation. Hydrogen
transfer can also occur without direct hydrogen supply in a catalytic
cracking reaction. This is possible by exploiting the right catalyst that
would initiate the hydrogen-transfer reaction. Furthermore, hydrogen
could also be generated in-situ via water gas shift (WGS) reaction by
using active WGS catalyst. Based on the reported literature, nickel

Table 1
Literatures on the catalytic cracking of vegetable oils for biogasoline production.
Catalyst Feedstock Reactor Yield (%) Reference

HZSM-5 Palm oil Fixed bed 48.5 Twaiq et al. (2004)

HZSM-5/Al2O3 Palm oil Fixed bed 47 Bhatia et al. (2009)
E-cat Cottonseed oil Fluidized bed 33.7 Li et al. (2009)
nano-ZSM-5 Used palm oil Fixed bed 37.05 Taufiqurrahmi et al. (2011)
H-AlMCM-41 Palm oil Fixed bed 29.4 Suyanta and Izul (2012)
HZSM-5 Palm oil Fixed bed 28.87 Sirajudin et al. (2013)
USY/ZSM-5 Sunflower oil Fixed bed 43.5 Doronin et al. (2014)
HZSM-5, Jatropha oil Fixed bed 50 Ramya et al. (2015)
H2SO4 Rubber seed oil Batch 48.3 Rengga et al. (2015)
V2O5 Sunflower oil Batch 29.2 Yigezu and Muthukumar (2015)
FeZnCuZSM-5 Palm oil Batch 59 Ahmad et al. (2016)
ZSM-5 Soybean oil Fixed bed 32.21 Emori et al. (2017)
USY Jatropha oil Fluidized bed 38.61 Zheng et al. (2017)
ZSM-5 Rubber seed oil Batch 34.86 Hassan et al. (2017)
E-cat Sunflower oil Fixed bed ≈40 Shimada et al. (2018)
HZSM-5 Waste cooking oil Fixed bed 35.0 Vu and Armbruster (2018)
HY Palm oil Fixed bed 34.25 Istadi et al. (2019)
ZSM-5 Palm oil Fixed bed 42.6 Makertihartha et al. (2020)

2
H.K. Gurdeep Singh, et al.
Fig. 1. Inconel batch reactor diagram (Chan et al., 2015).
Product (wt . )
Liquid or gas or coke product yield (%) = × 100
Linoleic acid fed (wt . )
Area of gasoline or above C or oxygenates
OLP composition (%) =
Total area of liquid
Area of PIONA compounds
Gasoline composition (%) = × 100
Area of gasoline
catalyst promotes deoxygenation activity and produce a large amount
of H2 gas during the catalytic pyrolysis of biomass in the presence of
steam (Kantarelis et al., 2014). The insitu hydrogen generation in water
gas shift (WGS) reaction, shifts the hydrogen limited environment to the
carbon-limited environment. The findings of Schaidle et al. (2015),
proves that Cu-modified BEA zeolite could produce high-value gasoline
range alkanes via hydrogen integration simultaneously reducing the
aromatics yield.
Based on literature review, so far limited literature has reported on
the catalytic cracking of model compound of rubber seed oil that is
linoleic acid for biogasoline production. Studying the model compound
gives a better understanding of the process and reaction routes.
Therefore, this study aims to investigate the catalytic cracking of lino-
leic acid using HZSM5 as support, monometallic nickel and copper
doped over HZSM-5 and pure copper metal as catalyst in order to in-
crease the isoparaffin compounds and decrease the aromatics and
oxygenates in the gasoline fraction.
2. Materials and methods
2.1. Materials
The zeolite ZSM-5 in its ammonium form was obtained from Alfa
Aesar, USA. The copper (II) chloride dehydrate (99.0%) and nickel (II)
chloride hexahydrate (98.0%) as metal precursors as well as the feed-
stock linoleic acid (98.0%) were procured from Wako Chemicals,
Japan.
2.2. Catalyst preparation
Initially, the ZSM-5 in ammonium form was calcined at 550 ᵒC for
6 h forming HZSM-5. Later, 5 wt% of nickel and copper in HZSM-5 were
prepared using wet impregnation method (Vichaphund et al., 2015)
using copper (II) chloride dihydrate and nickel (II) chloride hexahy-
drate solutions respectively. Subsequently, both the mixtures were
stirred at 80ᵒC for 2 h. Then, the concentrated mixtures formed were
kept to dry overnight at 100ᵒC. The resulted Ni/ZSM-5 and Cu/ZSM-5
powders obtained later undergo calcination for 5 h at 540ᵒC in a fur-
nace.
Environmental Research 186 (2020) 109616
(1)
× 100
(2)
(3)
2.3. Catalyst characterisation
The X-ray Diffraction (XRD) patterns used to study the structure of
the catalysts were obtained from Rigaku X-ray diffractometer. The XRD
patterns, were assessed at a range of 5ᵒ to 80ᵒ. The average crystallite
size was measured using Scherer's equation (Ameen et al., 2019). The
functional groups were determined by Fourier Transform Infrared
Spectroscopy (FTIR) using JASCO FTIR-4100. The wavelength was kept
in the range of 4000 to 400 cm⁻ˡ. The field emission electron microscopy
(FESEM) analysis was performed to study the catalyst morphology
using Zeiss Supra 55 VP instrument. The surface area and pore property
were examined by nitrogen adsorption-desorption method (BET ana-
lysis) using Surface Area Analyzer and Porosimetry System, Model:
Micromeritics ASAP 2020.
The characterization of the acid sites present on the catalyst was
studied using Temperature-Programmed Desorption of ammonia (NH3-
TPD) analysis. The apparatus used was Model: TPD/R/O 1110. The
sample was pretreated at 500 ᵒC for 1 h under helium flow of 20 cm3/
min. After that, it was set to cool before saturating it for 30 min under
NH3 flow. Later, the sample was purged with helium again to remove
any physiosorbed NH3 before conducting NH3 desorption up to 550 ᵒC
with a heating rate of 10 ᵒC/min.
2.4. Catalytic cracking of linoleic acid
In this study, catalytic cracking approach was used to produce ga-
soline range hydrocarbons. The experiment was designed based on the
optimum condition reported by Rengga et al. (2015) on the catalytic
cracking of crude RSO over H2SO4 in a batch reactor. The experiment
was conducted under an atmospheric condition in an 8.8 mL Inconel
batch reactor as presented in Fig. 1. First, 0.5 wt% of catalyst were
introduced into the 4 mL of linoleic acid present in the Inconel batch
reactor. Then, the electric furnace temperature was set to 450 ᵒC. Once
the temperature stabilised, the Inconel batch reactor was placed into
the electric furnace and the reaction was commenced for 90 min. As
soon as the reaction completes, the reactor was immediately condensed
in a bucket of water. After a while, centrifugation was carried out to
separate the solid from the liquid product. Then, once the liquid pro-
duct settles into 2 phase, the organic phase was segregated from the
aqueous phase for further analysis using GCMS model HP6890 series
3
H.K. Gurdeep Singh, et al.
Fig. 2. XRD patterns of HZSM-5, Cu/ZSM-5 and Ni/ZSM-5.
with a HP-5MS capillary glass column (30 m long x 250 μm ID x
0.25 μm film thickness).
The compounds present in the organic liquid product (OLP) were
grouped into gasoline range hydrocarbons (C5–C12), above C12 hydro-
carbons and oxygenates. Further analysis of gasoline composition was
conducted based on PIONA grouping. The products distribution, OLP
composition and gasoline composition were calculated based on equa-
tions (1)–(3) respectively.
3. Results and discussion
3.1. Catalyst characterisation
3.1.1. XRD analysis
Fig. 2 illustrates the effect of incorporating metal in parent HZSM-5
on the catalyst structure. It was observed that metal addition did not
distort the XRD pattern of parent HZSM-5. Both metal deposited cata-
lysts still resemble their parent catalyst structure. Thus, preserving the
crystallinity of the catalyst. However, their intensities were reduced
with the addition of metal. The presence of copper was seen at peak
angles 43.1ᵒ, 50.2ᵒ and 73.7ᵒ while the presence of nickel was located at
peak angles 44.4ᵒ, 51.8ᵒ and 76.3ᵒ. The HZSM-5 characteristic peaks in
all the catalysts were verified by the presence of peaks in the range of
2θ = 7-10ᵒ and 23-25ᵒ (Bayat and Sadrameli, 2017).
3.1.2. FTIR analysis
The FTIR spectrums displayed in Fig. 3 is consistent with the XRD
pattern obtained. The metal impregnated catalyst showed similar trend
as compared to their parent HZSM-5 catalyst. Hence, the addition of
metals did not significantly affect the functional groups present in the
parent catalyst but experienced slight decreased in transmittance in-
tensity. The peaks at approximate wavelengths of 3620 cm−1,
1640 cm−1, 1220 cm−1, 1100 cm−1, 800 cm−1, 550 cm−1 and
450 cm−1 represent acidic hydroxyl groups, water bending vibration,
external asymmetric stretch, internal asymmetric stretch, external
symmetric stretch, double ring and internal tetrahedral bending vi-
bration respectively (Zhao et al., 2015a).
3.1.3. FESEM analysis
Fig. 4 shows the morphologies of parent HZSM-5 and the metal
deposited HZSM-5 (copper and nickel) catalysts. The SEM image of
HZSM-5 particles structure in Fig. 4a exhibited defined cubic crystal
shape. This is consistent with the study reported by (Vichaphund et al.,
2015). However, in the other two images (Fig. 4b and c), it was noticed
4
Environmental Research 186 (2020) 109616
Fig. 3. FTIR spectra of HZSM-5, Cu/ZSM-5 and Ni/ZSM-5.
that the addition of metal affects the crystallinity of the parent catalyst.
Hence, irregularities in the catalysts morphologies were observed due
to sintering effect. Ahmad et al. (2016) also encountered similar effects.
Nevertheless, all the catalysts formed agglomerates because the crys-
tallite size obtained from XRD presented in Table 2 was considerably
less than 1–2 μm (Miskolczi et al., 2019).
The irregularities of the crystals observed after metal loading on
parent HZSM-5 changed the size and shape of the channels and con-
sequently affected the gasoline selectivity and PIONA distribution for
the catalytic cracking of vegetable oils. Among the metal deposited
catalysts, Cu/ZSM-5 showed less deterioration in crystals quality, which
matched with the findings of Round et al. (2001). This was supported
by the dot mapping analysis which demonstrated that copper species
was uniformly distributed compared to nickel species on the external
surface of parent HZSM-5. Lesser dispersion was observed in Ni/ZSM-5
was primarily due to its bigger aggregate crystallite size in comparison
to Cu/ZSM-5.
3.1.4. BET analysis
Fig. 5 illustrates the N2 physisorption curves of Cu/ZSM-5, Ni/ZSM-
5 and parent HZSM-5. It is apparent that the modified HZSM-5 and the
parent catalysts exhibit Type 1 isotherm, which signifies microporous
solid. This is because the catalysts showed linear gas adsorption at a
very low relative pressure forming a steep knee. After that, the gas
adsorption gradually decreases as relative pressure increases creating a
long horizontal plateau due to micropore filling (Wuamprakhon et al.,
H.K. Gurdeep Singh, et al. Environmental Research 186 (2020) 109616

Fig. 4. FESEM couple with dot mapping of (a) HZSM-5, (b) Cu/ZSM-5 and (c) Ni/ZSM-5.

2016). However, by introducing metals such as copper and nickel into Thus, it can be assumed that most of the metal would have been ad-
HZSM-5 the quantity of gas adsorbed reduced. Similarly, the specific sorbed only the external surface of HZSM-5 (Zhao et al., 2015b). On the
surface area also reduced with the metal impregnation nevertheless other hand, the average pore size increased slightly for both the metal
almost negligible change in the pore volume was observed in Table 2. modified HZSM-5 probably due to the blockage of metal species on the

5
H.K. Gurdeep Singh, et al. Environmental Research 186 (2020) 109616

Table 2
Surface area, porosity, aggregate crystallite size and acidity of HZSM-5, Ni/ZSM-5 and Cu/ZSM-5.
Catalyst Surface area (m2g−1) Pore Volume (cm3g−1) Pore size (nm) Aggregate crystallite size (nm) Acidity amount (μmol/g)

HZSM-5 432 0.262 2.43 21.5 6798.68

Ni/ZSM-5 400 0.264 2.63 26.5 7545.89
Cu/ZSM-5 391 0.258 2.63 19.5 7026.58

proton mobility in zeolites. On the other hand, the second peak ob-
served at high temperature region (400–600 ᵒC) signified the presence
of strong acid sites (Li et al., 2018). These peaks usually described
desorption of strongly bonded ammonia on Brønsted acid sites
(Rodríguez-González et al., 2007).
At low-temperature region parent HZSM-5 showed the highest
desorption peak however when metal like Cu and Ni were added the
desorption intensities reduced. In contrary, the metal-doped catalyst
exhibited higher desorption intensities than its parent catalyst at a
higher temperature region. Among them, Ni/ZSM-5 was the highest.
The acidity amount displayed in Table 2 further confirms the findings
obtained. Furthermore, the addition of metal also shifted the strong
acidic peaks to a higher temperature. The shifting was probably at-
tributed by the replacement of H+ with Cu2+ and Ni2+ respectively
which had affected the acidity of the catalyst. A similar trend was also
observed by Li et al. (2018).

3.2. Liquid, gas and coke distribution

Fig. 5. N2 adsorption-desorption isotherms of HZSM-5, Cu/ZSM-5 and Ni/ZSM-
5.
micropores. Similar findings were reported by Zakaria et al. (2012) and
Gulec et al. (Guleç et al., 2019).
3.1.5. NH3TPD analysis
Fig. 6 shows NH3-TPD profiles of HZSM-5, Cu/ZSM-5 and Ni/ZSM-5
catalysts. The desorption peaks seen at two temperature regions at-
tributed to the presence of Brønsted and Lewis acid sites in the zeolite
structure (Sandoval-Díaz et al., 2015). The peaks observed at low
temperature region (100–300 ᵒC) usually represent weak Lewis acid
sites of zeolites which correspond to desorption of weakly bonded
ammonia. The concentration of this site has no significance effect on
the catalytic processes however, assumed to effectively facilitates the
The product distribution of Ni/ZSM-5 and Cu/ZSM-5 were com-
pared to its parent HZSM-5 catalyst. The performance of pure copper
catalyst against copper-doped HZSM-5 was also tested. In terms of
product distribution as depicted in Fig. 7, it is observed that Ni/ZSM-5
gave an opposite effect than Cu/ZSM-5 relative to its parent HZM-5.
Cu/ZSM-5 increased the liquid yield but reduced the gas and coke yield
while Ni/ZSM-5 showed the opposite trend. The similar result was
observed for Ni/ZSM-5 in comparison to ZSM-5 by Dewajani et al.
(2016) during the cracking of Nyamplung oil.
The product distributions were influenced by the catalyst properties
because after metal impregnation with copper and nickel, the proper-
ties of the parent HZSM-5 changed. The catalyst properties that affected
the catalytic cracking activity were mainly acidity and surface area (Li
et al., 2018). Metal addition such as copper and nickel were reported to
increase the Lewis acid sites in the parent HZSM-5 (Li et al., 2018). This
type of acid sites reduces vigorous secondary cracking of liquid into
gaseous products unlike Brønsted acid sites. This explained the high

Fig. 6. NH3-TPD profiles of HZSM-5, Cu/ZSM-5 and Ni/ZSM-5. Fig. 7. Liquid, gas and coke yield of HZSM-5, Ni/ZSM-5, Cu/ZSM-5 and Cu.

6
H.K. Gurdeep Singh, et al.
liquid yield obtained for Cu/ZSM-5 but this was not true for Ni/ZSM-5,
though both had a high number acidic number sites. This is because, the
NH3TPD analysis for Ni/ZSM-5 showed that the catalyst had a higher
acidic strength than Cu/ZSM-5 due to the movement of the strong
acidic peaks to a much a higher temperature observed in Ni/ZSM-5
catalyst. As a result, the secondary cracking reactions occurred robustly
in Ni/ZSM-5 which led to lowest liquid yield.
In addition, other by-product such as coke is also produced during
the catalytic cracking reaction. A slightly higher coke yield was noticed
in Ni/ZSM-5 compared to HZSM-5 and Cu/ZSM-5. The increased in the
pore size together with the stronger Lewis acid sites found in the Ni/
ZSM-5 produced higher coke yield. This was because the increase in
pore size allowed higher accessibility of hydrocarbons to the pores
which resulted in polycondensation reactions that transpired the for-
mation of heavy molecular weight hydrocarbons causing coke forma-
tion (Kantarelis et al., 2019). Furthermore, the presence of stronger
Lewis acid sites acted as active sites to promote dehydrogenation re-
action in the absence of hydrogen which resulted in the formation of
coke precursor species on the catalyst surface (Triwahyono et al.,
2011).
Therefore, the synergistic effect of copper with HZSM-5 resulted in
better performance on the product distributions compared to the stand-
alone copper catalyst, Ni/ZSM-5 and parent HZSM-5 catalyst. To fur-
ther evaluate the effectiveness of these catalysts in promoting gasoline
range hydrocarbons formation, the liquid composition obtained for
each catalyst was discussed in the following section.
3.3. Organic liquid product (OLP) distribution
Fig. 8 illustrates the OLP compositions obtained for each catalyst
studied. It can be observed that gasoline range hydrocarbons (C5–C12)
gradually increased with metal impregnation both for Ni/ZSM-5 and
Cu/ZSM-5 relative to its parent HZSM-5 probably due to the increase in
the number of active acid sites available on the catalyst (Ahmad et al.,
2016). The presence of Brønsted acid sites as well as newly added Lewis
acid sites after metal modification of HZSM-5 promoted the cracking
reaction of long chain linoleic acid into gasoline range hydrocarbons
(Ahmad et al., 2016). However, the increment was not drastic even
after the addition of metal in HZSM-5. This explains that metal im-
pregnation did not give a major impact on the gasoline distribution in
OLP but influenced the PIONA compounds distribution in gasoline as
seen in Fig. 9.
Taufiqurrahmi & Bhatia (Taufiqurrahmi and Bhatia, 2011) ex-
plained the catalytic cracking mechanism of oils which resulted in the
organic liquid product distribution. The first step initiates the thermal
breakdown of heavy oxygenated hydrocarbons such as fatty acids that
are present in the vegetable oils to oxygenated hydrocarbons and heavy
Fig. 8. OLP composition of HZSM-5, Ni/ZSM-5, Cu/ZSM-5 and Cu.
7
Environmental Research 186 (2020) 109616
Fig. 9. Gasoline composition of HZSM-5, Ni/ZSM-5, Cu/ZSM-5 and Cu.
hydrocarbons. This primary cracking is presumed to occur in the in-
ternal pores of the zeolites. The oxygenated compounds then undergo
deoxygenation to remove oxygen molecule via decarboxylation, dec-
arbonylation and dehydration reaction by emitting CO2, CO and H2O
respectively to form heavy hydrocarbons. The pure heavy hydrocarbon
chains then cracked to form lighter hydrocarbon chain known as par-
affin and olefins which can also be in a gaseous form during the sec-
ondary cracking reaction. The lighter hydrocarbons could further un-
dergo isomerization, cyclization and aromatization in the presence of
catalyst to form isoparaffins, naphthenes and aromatics respectively in
the gasoline range. Further polymerization of aromatics resulted in
coke formation. The condensation of triglycerides could also resulted in
coke formation.
Nevertheless, gasoline range hydrocarbon represents the major
constitute of the organic liquid products for all the catalyst with lesser
relative abundance of other by products such as heavy hydrocarbons
(above C12) and oxygenates. It is noted that Cu/ZSM-5 and Ni/ZSM-5
catalyst experienced slight increment in the relative abundance of
heavy hydrocarbons in their liquid composition. This is because tran-
sition metals like copper and nickel on HZSM-5 provides ideal en-
vironment for oligomerisation reaction of shorter chain alkene due to
the bifunctional characteristic of the metal sites and acid sites which
consequently results to heavier hydrocarbon formation (Vichaphund
et al., 2015). However, between this two metal modified zeolites, Cu/
ZSM-5 showed the least affinity for oligomerisation.
Interestingly, the addition of copper and nickel in HZSM-5 lowered
the relative abundances of oxygenates in the liquid composition in
comparison to parent HZSM-5. This implies that metal modified HZSM-
5 shows a better deoxygenation tendency compared to the parent
HZSM-5. This concurs well with Vichapund et al. (Vichaphund et al.,
2015) findings. This is because the increase in the Lewis acid sites on
HZSM-5 with metal introduction enhances deoxygenation reaction of
oxygenated hydrocarbons (Ahmad et al., 2016). Among the catalysts
studied, Cu/ZSM-5 showed a superior performance in lowering the
oxygenated hydrocarbons while the stand-alone copper catalyst gave
the opposite results. This shows that the synergy effect of copper in
HZSM-5 improves the deoxygenating efficiency of the catalyst by low-
ering the relative abundance of oxygenates considerably from 34.7% to
15.4%. Larger relative abundance of oxygenates are undesirable as it
decreases the overall energy content of a fuel. As a result, for the same
driving cycle, a higher volumetric fuel is consumed (Martini et al.,
2013).
In conclusion, it confirms that Cu/ZSM-5 showed a highest deox-
ygenation tendency and gave the most gasoline range hydrocarbons as
compared to Ni/ZSM-5, parent HZSM-5 and copper catalyst. Hence, to
further evaluate the quality of the gasoline fraction, the discussion on
PIONA analysis were presented in the following section. Particularly,
relative abundances isoparaffin compounds were used as a basis to
describe the most potential catalyst for producing high quality gasoline.
H.K. Gurdeep Singh, et al.
3.4. PIONA and oxygenates distribution
The PIONA distribution was determined by percentage area nor-
malization technique, based on peak areas obtained from the GC
chromatograms. The remarkable correlation of copper in HZSM-5 that
was worth noting in Fig. 9, was the selectivity towards isoparaffin
compounds, in comparison to its parent HZSM-5. The value increased
from 1.6% to 6.8%. However, both Ni/ZSM-5 and copper catalyst
showed low selectivity towards isoparaffin compounds. It has been
suggested by Schaidle et al. (2015) that incorporation of copper in
HZSM-5 produce H2 naturally. The author claimed that the H2 was
produced via two ways. One is by the decomposition of dimethyl ether
(DME) on metallic copper, present on zeolite's external surface to pro-
mote H2 activation. While, the second way is through alkane dehy-
drogenation over Lewis acidic cationic copper sites, located within the
zeolite pores to enhance hydrogen transfer reaction.
Furthermore, the CO produced from DME decomposition and water
produced from DME homologation react in water-gas-shift (WGS) re-
action to form H2. Since copper is an active metal for WGS reaction, it
will enhance the H2 production. Therefore, employing the same prin-
ciple in catalytic cracking which gives the same by-products CO and
H2O (deoxygenation reaction by-products) over metallic copper, could
also produce H2. Hence initiating hydrogenation even in the absence of
H2 supply. This seems to be an innovative approach for saturating the
polyunsaturated feedstock like linoleic acid. Consequently favouring
branched alkane (isoparaffin) formation derived from the hydrogena-
tion of C4 – C7 olefins through olefin catalytic cycle (Schaidle et al.,
2015). Alongside, slight increase in naphthenic and paraffinic com-
pounds were observed.
Ultimately, with the increased in the isoparaffin compounds, aro-
matics compounds decreased in Cu/ZSM-5 (59.7%) as compared to
both HZSM-5 (76.4%) and Ni/ZSM-5 (69.0%). This was probably due to
decreased in the polycyclic aromatic hydrocarbons (PAH) formation,
produced via Diels-Alder reaction (Widayatno et al., 2016). Apart from
that, the drop in the aromatics compounds might also be due to the
addition of metal in zeolite (Vichaphund et al., 2014). That is the
reason that the aromatics compounds for Ni/ZSM-5 decreased even
though it did not increase the isoparaffin compounds. On the contrary,
olefin compounds gradually increased in Cu/ZSM-5. This finding cor-
roborates with the explanation given by Schaidle et al. (2015). The
author discovered that copper modified zeolite without cofed H2
showed high selectivity for olefins by means of dehydrogenation reac-
tion.
In summary, the evidence from this PIONA analysis studies implies
that Cu/ZSM-5 is a potential catalyst for producing high quality bio-
gasoline from the catalytic cracking reaction of linoleic acid which is a
model compound of RSO. The considerable production of isoparaffins
in the gasoline fraction over Cu/ZSM-5 catalyst justifies the improve-
ment of the gasoline quality.
4. Conclusions
Catalytic cracking of linoleic acid was carried out in an Inconel
batch reactor at 450 ᵒC for 90 min at atmospheric condition. The effect
of HZSM-5, Cu/ZSM-5, Ni/ZSM-5 and copper catalyst in favouring ga-
soline type hydrocarbons in terms of PIONA were investigated in order
to evaluate the quality of the gasoline produced. Among the catalyst
studied, Cu/ZSM-5 gave the highest liquid yield of 79.1%, at the same
time reduced the production of gas and coke to 18.8% and 0.7%.
Besides, both the Cu/ZSM-5 and Ni/ZSM-5 showed slight improvement
of gasoline relative content in the OLP in comparison to its parent
HZSM-5. However, the former had a greater impact than the latter in
favouring gasoline range hydrocarbons. Furthermore, the synergism
between copper and HZSM-5 promotes the desired isoparaffin produc-
tion. The value increased from 1.6% to 6.8%. In addition, both copper
and nickel modified HZSM-5 reduced the aromatics formation and
8
Environmental Research 186 (2020) 109616
promoted deoxygenation but the former gave a better result. Overall,
Cu/ZSM-5 showed superior performance in favouring gasoline-like
hydrocarbons especially isoparaffin by lowering the undesired aro-
matics and oxygenates formation. This was an initial screening stage in
determining the best modified zeolite in favouring isoparaffin in gaso-
line production from linoleic acid (model compound of RSO).
CRediT authorship contribution statement
Haswin Kaur Gurdeep Singh: Investigation, Writing - original
draft. Suzana Yusup: Supervision, Conceptualization, Funding acqui-
sition. Armando T. Quitain: Conceptualization, Resources. Bawadi
Abdullah: Resources. Mariam Ameen: Writing - review & editing.
Mitsuru Sasaki: Resources. Tetsuya Kida: Resources. Kin Wai Cheah:
Writing - review & editing.
Declaration of competing interests
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
This research was financially supported by the Ministry of Higher
Education (MOHE), Malaysia under the Long Term Research Grant
Scheme (LRGS) and Higher Institution Centre of Excellence (HICoE).
The authors also acknowledge supports from the two collaborating
universities - Universiti Teknologi PETRONAS (Malaysia) and
Kumamoto University (Japan).
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